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Herein we successfully utilize various directing groups to achieve a ligand-enabled nickel-catalyzed 1,2-borylalkylation of unactivated alkenes. A β-amino alcohol was employed as the ligand for non-asymmetric 1,2-borylalkylation of unactivated alkenes, while a bulky chiral diamine ligand was used to achieve the asymmetric 1,2-borylalkylation of allyl amides.

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Herein, a nickel-catalyzed divergent reductive-Heck reaction of 1-bromo-2-((2-(aryl/alkyl ethynyl)phenoxy)methyl)benzene and 2-(aryl/alkyl ethynyl)phenyl 2-bromobenzenesulfonate derivatives has been demonstrated through the regulation of reducing agents and solvent systems. This scalable protocol offers regio- and stereoselective access to functionalized dibenzo[,]oxepine and dibenzo[,][1,2]oxathiepine 6,6-dioxide scaffolds in high to excellent yields under a mild set of reaction conditions. This methodology offers a predictable route for the synthesis of medium ring oxygen heterocycles and demonstrates wide substrate scope and outstanding tolerance to various functional groups like hydroxyl and, of course, practical instance via the synthesis of doxepin and nordoxepin molecules.

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Article Synopsis
  • Site-specific modifications of glycosides can significantly enhance drug properties, but creating versatile glycoside building blocks from sugar precursors is challenging.
  • A new nickel-catalyzed carboboration method allows for selective modifications at C1 and C2 positions, improving the ability to create diverse glycosides.
  • This approach offers a universal method to quickly generate various rare sugars, accommodating different functional groups and showing potential for synthesizing analogs of natural products and pharmaceuticals.
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Nickel-Catalyzed Atroposelective Carbo-Carboxylation of Alkynes with CO: En Route to Axially Chiral Carboxylic Acids.

Angew Chem Int Ed Engl

January 2025

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu, 610064, P. R. China.

Precise synthesis of carboxylic acids via catalytic carboxylation with CO is highly appealing. Although considerable advancements have been achieved in difunctionalizing carboxylation of unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly in addressing axially chiral alkenes. Herein, we report the first catalytic atroposelective carboxylation of alkynes with CO.

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Regio- and Enantioselective Nickel-Catalyzed Ipso- and Remote Hydroamination Utilizing Organic Azides as Amino Sources for the Synthesis of Primary Amines.

J Am Chem Soc

November 2024

State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.

Primary amines serve as key synthetic precursors to most other -containing compounds, which are important in organic and medicinal chemistry. Herein, we present a NiH-catalyzed mild ipso- and remote hydroamination technique that utilizes organic azides as deprotectable primary amine sources. This strategy offers a highly flexible platform for the efficient construction of α-chiral branched primary amines, as well as linear primary amines.

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